Structure and piezoelectric properties of 1-μm-thick polar-axis-oriented CaBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> films

1-μm-thick polar-axis-oriented CaBi₄Ti₄O₁₅ (CBTi144) films were fabricated by control of nucleation and growth in alkoxy-derived non-crystalline layers on Pt foils. The oxygen ambient during pre-baking impacted both the cross-sectional microstructure and the crystallographic orientation. The 1-μm-thick film showed relatively high intensities of (100)/(010) diffraction lines in the X-ray diffraction profile and simultaneously had a closely packed dense structure in the transmission electron microscopy cross-sectional profile. Resultantly, the leakage current density decreased to about 7×10^-8 A/cm² at 10 V. The piezoelectric constant d₃₃ was determined to be 260 pm/V at a maximum poling voltage of 60 V by measurements using piezoelectric force microscopy. PACS 77.55.+f; 77.84.-s; 77.65.-j; 68.55.Jk     

Effect of doping on the crystal structure and dielectric properties of the Aurivillius phase CaBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript>

The effect of doping on the crystal structure and dielectric properties of layered perovskite-type bismuth oxide CaBi₄Ti₄O₁₅ (Aurivillius phase) has been investigated. Partial substitution both in A (Bi by Na, Pb) and B (Ti by Cr, V, Re) sites leads to changes in the crystal structure parameters and dielectric constants, depending on the dopant type and content.     

Ferroelectric and dielectric properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> thin films grown on Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> film layer

Ferroelectric and dielectric properties of bilayered ferroelectric thin films, SrBi₄Ti₄O₁₅ grown on Bi₄Ti₃O₁₂, were investigated. The thin films were annealed at 700°C under oxygen atmosphere. The bilayered thin films were prepared on a Pt(111)/Ti/SiO₂/Si substrate by a chemical solution deposition method. The dielectric constant and dielectric loss of the bilayered thin films were 645 and 0.09, respectively, at 100 kHz. The value of remnant polarization (2P _r) measured from the ferroelectric thin film capacitors was 60.5 μC/cm² at electric field of 200 kV/cm. The remnant polarization was reduced by 22% of the initial value after 10¹⁰ switching cycles. The results showed that the ferroelectric and dielectric properties of the SrBi₄Ti₄O₁₅ on Bi₄Ti₃O₁₂ ferroelectric thin films were better than those of the SrBi₄Ti₄O₁₅ grown on a Pt-coated Si substrate suggesting that the improved properties may be due to the different nucleation and growth kinetics of SrBi₄Ti₄O₁₅ on the c-axis-oriented Bi₄Ti₃O₁₂ layer or on the Pt-coated Si substrate.     

Preparation and electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>4</Subscript>O<Subscript>7</Subscript> composite for lithium-ion batteries

In order to improve the rate capability of Li₄Ti₅O₁₂, Ti₄O₇ powder was successfully fabricated by improved hydrogen reduction method, then a dual-phase composite Li₄Ti₅O₁₂/Ti₄O₇ has been synthesized as anode material for lithium-ion batteries. It is found that the Li₄Ti₅O₁₂/Ti₄O₇ composite shows higher reversible capacity and better rate capability compared to Li₄Ti₅O₁₂. According to the charge-discharge tests, the Li₄Ti₅O₁₂/Ti₄O₇ composite exhibits excellent rate capability of 172.3 mAh g^?1 at 0.2 C, which is close to the theoretical value of the spinel Li₄Ti₅O₁₂. More impressively, the reversible capacity of Li₄Ti₅O₁₂/Ti₄O₇ composite is 103.1 mAh g^?1 at the current density of 20 C after 100th cycles, and it maintains 84.8% of the initial discharge capacity, whereas that of the bare spinel Li₄Ti₅O₁₂ is only 22.3 mAh g^?1 with a capacity retention of 31.1%. The results indicate that Li₄Ti₅O₁₂/Ti₄O₇ composite could be a promising anode material with relative high capacity and good rate capability for lithium-ion batteries.     

Electrical properties of Sr<Subscript>3</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>6</Subscript>O<Subscript>21</Subscript> thin films

Highly c-axis-oriented Sr₃Bi₄Ti₆O₂₁ (SBTi) thin films were fabricated on Pt-coated Si substrates by pulsed laser deposition (PLD). The structures were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and scanning electron microscopy (SEM). No peaks of SrTiO₃ (STO) could be detected in the XRD pattern, indicating the existence of the SBTi single phase. Good ferroelectric hysteresis loops of the films with Pt electrodes were obtained. With an applied field of 400 kV/cm, the measured remanent polarization (P_r) and coercive field (E_c) values were 4.1 C/cm² and 75 kV/cm respectively. The films showed little fatigue after 2.22×10⁹ switching cycles: the nonvolatile polarizations decreased by less than 5% of the initial values. The dielectric constant and the loss tangent of the films were measured to be 363 and 0.04 at 100 kHz. These results might be advantageous for nonvolatile ferroelectric random access memory (NVFRAM) and dynamic random access memory (DRAM). PACS 77.84.Dy; 77.22.-d; 68.55.Jk     

Electronic structure,ferroelectricity and optical properties of CaBi<Subscript>2</Subscript>Ta<Subscript>2</Subscript>O<Subscript>9</Subscript>

Using first-principles calculations based on density-functional theory in its local-density approximation, we investigated the Electronic structure, ferroelectricity and optical properties of CaBi₂Ta₂O₉ (CBT) for the first time. It is found that CBT compound has an indirect band gap of 3.114 eV and the O 2s and 2p states are strongly hybridized with the 6s states of Bi which belong to the (Bi₂O₂)²⁺ planes. The quite strong Ta–O and Bi–O hybridization is the primary source for ferroelectricity. Our results imply that the interaction between Bi and O is highly covalent. The anisotropy occurs mainly above 4 eV in the optical properties. The different optical properties have been discussed.     

Electric and magnetic properties of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript> bilayer thin films prepared by pulsed-laser deposition

CoFe₂O₄ (CFO) thin film with highly (111)-preferential orientation was first deposited on the silicon substrate by a pulsed-laser deposition, and then Pb(Zr_0.52Ti_0.48)O₃ (PZT) layers were deposited with different oxygen pressures to form the bilayer CFO/PZT nanocomposite thin films. X-ray diffraction showed that the PZT preferential orientation was strongly dependant on the oxygen pressure. The smooth film surface was obtained after depositing the CFO and PZT layers. The bilayer thin films exhibit good ferromagnetic and ferroelectric properties, and a low leakage current density of 0.004 μA/cm² at 50 kV/cm. The leakage current density curves show loops for the electric polarized field when the electric field reverses. PACS 77.84.Lf; 75.80+q; 81.05.Zx; 81.15.Fg     

Effects of dopant on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials

The effects of dopant on the electrochemical properties of spinel-type Li_3.97M_0.1Ti_4.94O₁₂ (M = Mn, Ni, Co) and Li_(4-x/3)Cr_xTi_(5-2x/3)O₁₂(x = 0.1, 0.3, 0.6, 0.9, 1.5) were systematically investigated. Charge-discharge cycling were performed at a constant current density of 0.5 mA/cm² between the cut-off voltages of 3.0 and 1.0 V, the experimental results showed that Cr³⁺ dopant improved the reversible capacity and cycling stability over the pristine Li₄Ti₅O₁₂. The substitution of the Mn³⁺ and Ni³⁺ slightly decreased the capacity of the Li₄Ti₅O₁₂. Dopants such as Co³⁺ to some extent worsened the electrochemical performance of the Li₄Ti₅O₁₂.     

Structural disordering in Cr-doped Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> spinels

The processes of lithium redistribution in the structure of cubic Li₄Ti₅O₁₂ spinel, caused by both chromium doping and thermal activation, have been investigated by nuclear magnetic resonance. It is shown that Li ions migrate from tetra- to octahedral crystallographic positions with an increase in temperature. This process becomes more pronounced at temperatures above 400 K. In contrast, the fraction of tetrahedrally coordinated Li increases as a result of doping with chromium.     

Integrated investigation of the Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> phase stability

The Li₄Ti₅O₁₂ is applied in lithium ion batteries as anode material, which can be synthesized by various synthesis techniques. In this study, the molten salt synthesis technique at low temperatures, i.e. 350 °C, was applied to synthesize Li₄Ti₅O₁₂. Surprisingly, the Li₄Ti₅O₁₂ was not formed according to XRD analysis, which raised question about the stability range of Li₄Ti₅O₁₂. To investigate the stability of Li₄Ti₅O₁₂ at low temperatures, the high-temperature calcined Li₄Ti₅O₁₂ powder was equilibrated in the LiCl-KCl eutectic salt at 350 °C. The result of experiment revealed that the Li₄Ti₅O₁₂ is not decomposed. Results of ab initio calculations also indicated that the Li₄Ti₅O₁₂ phase is a stable phase at 0 K. The products of molten salt synthesis technique were then annealed at 900 °C, which resulted in the Li₄Ti₅O₁₂ formation. It was concluded that the Li₄Ti₅O₁₂ is a stable phase at low temperatures and the reasons for not forming the Li₄Ti₅O₁₂ by molten salt technique at low temperature are possibly related to activation energy and kinetic barriers. The Li₄Ti₅O₁₂ formation energy is also very small, due to the results of ab initio calculations.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

Influence of K<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>13</Subscript> on dielectric and barrier properties of polymer

Polymer composite comprising polyvinylidene fluoride (PVDF) and potassium hexatitante (K₂Ti₆O₁₃) was synthesized by solution casting. The effect of K₂Ti₆O₁₃ on surface, thermal, and electrical properties of polymer composite were investigated. The addition of K₂Ti₆O₁₃ with polymer leads to thermal degradation and transition of polymer composite from semi-crystalline to amorphous phase. The optimum results of contact angle for different loading wt% of K₂Ti₆O₁₃ were directly correlated with the surface morphology. Our experimental results confirmed the incorporation of K₂Ti₆O₁₃ in polymer by SEM micrographs. The evaluated dielectric properties (ε' = 424; tan δ = 2.14 at 130 °C and 100 Hz frequency for 20 wt% loading of K₂Ti₆O₁₃) for polymer composite are higher in compared to pure polymer. The enhancement in dielectric constant and changing the surface properties of polymer composite can be used for the development of electrochemical storage device applications.     

Influence of cooling mode on the electrochemical properties of Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> anode materials for lithium-ion batteries

Li₄Ti₅O₁₂ (LTO) was synthesized with two different cooling methods by solid-state method, namely fast cooling and air cooling. The samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), galvanostatic charge–discharge test, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), respectively. XRD revealed that the basic LTO structure was not changed. FESEM images showed that fast cooling effectively reduced the particle sizes and the agglomeration of particles. Galvanostatic charge–discharge test showed that the air cooling sample exhibited a mediocre performance, having an initial discharge capacity of 136.3mAh?·?g^?1 at 0.5 C; however, the fast cooling sample demonstrated noticeable improvement in both of its discharge capacity and rate capability, with a high initial capacity value of 142.7 mAh?·?g^?1 at 0.5 C. CV measurements also revealed that fast cooling enhanced the reversibility of the LTO. EIS confirmed that fast cooling resulted in lower electrochemical polarization and a higher lithium-ion diffusion coefficient. Therefore, fast cooling have a great impact on discharge capacity, rate capability, and cycling performance of LTO anode materials for lithium-ion batteries.     

Processing and some properties of biferroic Bi<Subscript>5</Subscript> Ti<Subscript>3</Subscript> FeO<Subscript>15</Subscript> ceramics

Bi₅Ti₃FeO₁₅ (BTF) is an example of bifferoic Aurivillius phase with perovskite layered structure. Materials on the basis BTF are of substantial interest for new types of magnetoelectric device applications. In this review we discuss technology of preparation biferroic ceramic with composition Bi₅Ti₃FeO₁₅. The ferroelectric layered Bi₅Ti₃FeO₁₅ (BTF) Aurivillius phases were synthesized by solid-phase synthesis reaction from the conventional mixture of oxides, viz. Bi₂O₃, Fe₂O₃, TiO₂. Thermal analysis and mass change efect were used to investigate synthesis effects in the stoichiometric mixture of powders. The crystalline structure was checked by X-ray diffraction method at room temperature. Microstructure was investigated by scanning electron microscopy.     

Nano Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> as sulfur host for high-performance Li-S battery

S/Li₄Ti₅O₁₂ cathode with high lithium ionic conductivity was prepared for Li-S battery. Herein, nano Li₄Ti₅O₁₂ is used as sulfur host and fast Li⁺ conductor, which can adsorb effectively polysulfides and improve remarkably Li⁺ diffusion coefficient in sulfur cathode. At 0.5 C, S/Li₄Ti₅O₁₂ cathode has a stable discharge capacity of 616 mAh g^?1 at the 700th cycle and a capacity loss per cycle of 0.0196% from the second to the 700th cycle, but the corresponding values of S/C cathode are 437 mAh g^?1 and 0.0598%. Even at 2 C, the capacity loss per cycle of S/Li₄Ti₅O₁₂ cathode is only 0.0273% from the second to the 700th cycle. The results indicate that Li₄Ti₅O₁₂ as the sulfur host plays a key role on the high performance of Li-S battery due to reducing the shuttle effect and enhancing lithium ionic conductivity.     

Magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> surface

The magnetic properties of the magnetite Fe₃O₄(110) surface have been studied by spin resolved Auger electron spectroscopy (SRAES). Experimental spin resolved Auger spectra are presented. The results of calculation of Auger lines polarization carried out on the basis of electronic state density are presented. Problems related to magnetic moments of bivalent (Fe²⁺) and trivalent (Fe³⁺) ions on the Fe₃O₄(110) surface are discussed. It is established that the deposition of a thin bismuth film on the surface results in significant growth of polarization of iron Auger peaks, which is due to additional spin-orbit scattering of electrons by bismuth atoms.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

First-principle calculations for electronic structure and bonding properties in layered Na<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>7</Subscript>

First-principles calculations of Na₂Ti₃O₇ have been carried out with density-functional theory (DFT) and ultrasoft pseudopotentials. The electronic structure and bonding properties in layered Na₂Ti₃O₇ have been studied through calculating band structure, density of states, electron density, electron density difference and Mulliken bond populations. The calculated results reveal that Na₂Ti₃O₇ is a semiconductor with an indirect gap and exhibits both ionic and covalent characters. The stability of the (Ti₃O₇)²⁻ layers is attributed to the covalent bonding of strong interactions between O 2p and Ti 3d orbitals. Furthermore, the O atoms located in the innerlayers interact more strongly with the neighboring Ti atoms than those in the interlayer regions. The ion-exchange property is due to the ionic bonding between the Na⁺ and (Ti₃O₇)²⁻ layers, which can stabilize the interlayers of layered Na₂Ti₃O₇ structure.     

Preparation and electrical properties of Bi<Subscript>3.25</Subscript>Pr<Subscript>0.75</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ferroelectric thin films

Bi_3.25Pr_0.75Ti₃O₁₂ (BPT) ferroelectric thin films have been prepared by chemical solution deposition on platinized Si substrates. Well-crystallized BPT films can be achieved by 600 °C rapid thermal annealing. The film surface is smooth and crack-free, composed of uniform spherical grains around 90–100 nm in diameter. The electrical properties of Pt/BPT/Pt thin film capacitors were characterized by hysteresis and impedance measurements. The remanent polarization of 700 °C annealed BPT films is around 20 C/cm² at 120-kV/cm stimulus field. The dielectric constant is around 380 at 10 kHz, 100-mV amplitude. The remanent polarization of BPT film showed a slight reduction, 10% of its original value, after 2.8×10⁹ cycles, while a 30% reduction of non-volatile polarization was observed. PACS 81.15.-z; 77.55.+f; 77.22.Gm